This invention is concerned with the utilization of two industrial by-products; namely Class F fly ash and cement kiln dust (hereinafter CKD). When finely divided or pulverized coal is combusted at high temperatures, for example, in boilers for the steam generation of electricity, the ash consisting of the uncombustible residue plus a small amount of residual combustible matter, is made up of two fractions, a bottom ash recovered from the furnace or boiler in the form of a slag-like material and a fly ash which remains suspended in the flue gases from the combustion until separated therefrom by known separatory techniques, such as electrostatic precipitation. This fly ash is an extremely finely divided material generally in the form of spherical bead-like particles, with at least 70% by weight passing a 200 mesh sieve and has a generally glassy state, resulting from fusion or sintering during combustion. As recognized in the American Society of Testing Materials (ASTM) specification designation C618-85 entitled "Fly Ash and Raw or Calcined Natural Pozzolan for Use as a Mineral Admixture in Portland Cement Concrete", fly ash is subdivided into two distinct classifications; namely, Class F and Class C. The definitions of these two classes are as follows:
"Class F--Fly ash normally produced from burning anthracite or bituminous coal that meets the applicable requirements for this class as given herein. This class fly ash has pozzolanic properties.
Class C--Fly Ash normally produced from lignite or subbituminous coal that meets the applicable requirements for this class as given herein. This class of fly ash, in addition to having pozzolanic properties, also has some cementitious properties. Some Class C flyashes may contain lime contents higher than 10%."
The latter reference to "pozzolanic properties" refers to the capability of certain mixtures which are not in themselves cementitious of undergoing a cementitious reaction when mixed with lime in the presence of water. Class C fly ash possesses direct cementitious properties as well as pozzolanic properties. ASTM C618-85 is also applicable to natural pozzolanic materials which are separately classified as Class N but are not pertinent here.
As the above quotation indicates, the type of coal to be combusted generally determines which class fly ash results, and the type of coal in turn is often dependent on its geographic origin. Thus, Class C fly ash frequently results from coals mined in the Midwest; whereas Class F fly ash often comes from coals mined in the Appalachian region. The ASTM specification imposes certain "chemical requirements" upon the respective fly ash classifications thereof which are set forth below for the relevant Classes F and C, including footnotes:
TABLE I-A ______________________________________ CHEMICAL REQUIREMENTS Mineral Admixture Class F C ______________________________________ Silicon dioxide (SiO.sub.2) plus aluminum 70.0 50.0 oxide (Al.sub.2 O.sub.3) plus iron oxide (Fe.sub.2 O.sub.3), min, % Sulfur trioxide (SO.sub.3), max, % 5.0 5.0 Moisture content, max. % 3.0 3.0 Loss on ignition, max, % .sup. 6.0.sup.1 6.0 ______________________________________ .sup.1 The use of Class F pozzolan containing up to 12.0% loss on ignitio may be approved by the user of either acceptable performance records or laboratory test results that are made available.
TABLE I-B ______________________________________ SUPPLEMENTAY OPTIONAL CHEMICAL REQUIREMENT Mineral Admixture Class F C ______________________________________ Available alkalies, as Na.sub.2 O, max, %.sup.2 1.50 1.50 ______________________________________ Note: This optional requirement applies only when specifically requested. .sup.2 Applicable only when specifically required by the purchaser for mineral admixture to be used in concrete containing reactive aggregate an cement to meet a limitation on content of alkalies.
The ASTM physical requirements for both fly ash classes are virtually the same and are reproduced below exclusive of cautionary footnotes:
TABLE I-C ______________________________________ PHYSICAL REQUIREMENTS Mineral Admixture Class F C ______________________________________ Fineness Amount retained when wet-sieved 34 34 on No. 325 (45 .mu.m) sieve, max % Pozzolanic activity index With portland cement, at 75 75 28 days, min. percent of control With lime, at 7 days min, 800(5500) . . . psi (kPa) Water requirement, max, 105 105 percent of control Soundness Autoclave expansion or contraction, 0.8 0.8 max % Uniformity requirements The specific gravity and fineness of individual samples shall not vary from the average established by the ten preceding tests or by all preceding tests if the number is less than ten, by more than: Specific gravity, max variation 5 5 from average, % Percent retained on No. 325 5 5 (45 .mu.m), max variation, percentage points from average ______________________________________
CKD, on the other hand, is a by-product of the production of portland cement clinkers by the high temperature furnacing of appropriate raw materials typically mixtures of limestone and clay or a low grade limestone already containing a sufficient quantity of argillaceous materials often with added quantities of lime to adjust the final composition. The resultant clinkers are pulverized by grinding to a high degree of fineness and these particles upon admixture with sufficient water undergo a cementitious reaction and produce the solid product generally referred to as concrete, which exhibits high compressive strength and is thus highly useful in the construction of a great variety of building or supporting structures. Generally, rotary furnaces are used for producing portland cement clinkers and a certain quantity of finely divided dust is produced as a by-product which is carried off in the flue gases from such furnaces. The dust content can range from about 5% of the clinkers output in so-called wet process plants up to as high as 15% in dry process plants. The suspended dust is removed by various separating techniques and remains as a by-product of the cement making operation. Part of the CKD can be returned to the furnace as recycled raw material, but it is not readily reincorporated into clinker formation and, in addition, tends to excessively elevate the alkalinity of the ultimate portland cement.
The quantities of these two by-product materials which are produced annually are enormous and are likely only to increase in the future. As petroleum oil as the fuel for the generation of electricity is reduced because of conservation efforts and unfavorable economics vs. the more readily available coal and as political considerations increasingly preclude the construction of new nuclear power electrical generating facilities, or even the operation of already completed units of this type, greater reliance will necessarily fall on coal as the fuel for generating electricity. As of 1979, the amount of CKD was estimated as accumulating at a rate of 4-12 million tons per year in the United States alone; whereas the amount of Class F fly ash that is available is estimated to be about ten times what can be readily utilized. Obviously, there is an urgent growing need to find effective ways of employing these unavoidably industrial by-products since otherwise they will collect at a staggering rate and create crucial concerns over their adverse environmental effect.
Various proposals have already been made for utilizing both fly ash and CKD. According to the text The Chemistry of Cement and Concrete by Lea, Chemical Publishing Company, Inc., 1971 edition, at page 421 et seq., fly ash, i.e., Class F type, from boilers was first reported to be potentially useful as a partial replacement for portland cement in concrete construction about 50 years ago, and its utilization for that purpose has since become increasingly widespread. It is generally accepted that the proportion of portland cement replaced by the usual fly ash should not exceed about 20% to avoid significant reduction in the compressive strength of the resultant concrete, although some more cautions jurisdictions may impose lower limits, e.g., the 15% maximum authorized by the Virginia Department of Highways and Transportation (VDHT). As described by Lea at page 437, the substitution of the fly ash tends to retard the early rate of hardening of the concrete so that the concrete shows up to a 30% lower strength after seven days testing and up to 25% lower strength after 28 days of testing, but in time the strength levels equalize at replacement levels up to 20%. Increasing the substitution quantity up to 30% gives more drastic reduction in the early compression values plus an ultimate reduction of at least about 15% after one year.
The limited substitution of fly ash for portland cement in concrete formulations has other effects beyond compressive strength changes, both positive and negative. The fly ash tends to increase the workability of the cement mix and is recognized as desirably reducing the reactivity of the portland cement with so-called reactive aggregates. On the other hand, fly ash contains a minor content of uncombusted carbon which acts to absorb air entrained in the concrete. Because entrained air increases the resistance of the hardened concrete to freezing, such reduction is undesirable but can be compensated for by the inclusion as an additive of so-called air-entraining agents.
Utilization of fly ash for up to 20% of cement in concrete mixes at best consumes only a fraction of the available quantities of this material, and efforts have been made to increase its use. Dodson et al in U.S. Pat. No. 4,210,457, while recognizing this accepted limit, proposed the substitution of larger amounts of fly ash, and preferably more, of the portland cement with certain selected natural fly ashes having a combined content of silica, alumina and ferric oxide content, less than 80% by weight, and a calcium content exceeding 10%, based on five samples of such ashes, varying from about 58-72% combined with a calcium oxide range of about 18-30%. Six other ash samples which were not suitable at the high levels of 50% or more were shown to vary in the combined oxide content from about 87-92% and in calcium oxide content from about 4 to about 8%. Evaluating these values against the ASTM C618-85, one observes that the acceptable fly ashes came under the Class C specifications, while the unacceptable ashes fell in the Class F specification. Thus, this patent in effect establishes that natural Class C fly ashes are suitable for substantially higher levels of replacement for portland cement in concrete mixes than are Class F fly ashes, and this capacity is now generally recognized, with Class C fly ashes being generally permitted up to about a 50% replacement level while maintaining the desirable physical properties of the concrete especially compressive strength.
In U.S. Pat. No. 4,240,952, Hulbert et al while also acknowledging the generally recognized permissible limit of (Class F) fly ash replacement for portland cement of 20%, proposed replacement of at least 50% up to 80%, provided the mix contained as additives about 2% of gypsum and about 3% of calcium chloride by weight of the fly ash. The fly ash described for this purpose, however, was a natural Class C fly ash analyzing about 28% calcium oxide and a combined silica, alumina and ferric oxide content of about 63%. With up to 80% of this fly ash and the specified additives, compressive strengths comparable to straight portland cement were said to be generally achievable. In one example using 140 pounds portland cement and 560 pounds of fly ash (80-20 ratio) with conventional amounts of coarse and fine aggregate, and water and including the requisite additives, compressive strengths tested at 3180 psi for 7 days, 4200 psi for 14 days and about 5000 psi at 28 days.
Obviously, the above patents cannot contribute to a solution to the problem with Class F fly ash. In U.S. Pat. Nos. 4,018,617 and 4,101,332, Nicholson proposed the use of mixtures of fly ash (apparently Class F in type), cement kiln dust and aggregate for creating a stabilized base supporting surface replacing conventional gravel- or asphalt-aggregate-stabilized bases in road construction wherein the useful ranges were fly ash 6-24%, CKD 4-16% and aggregate 60-90%, with 8% CKD, 12% fly ash and 80% aggregate preferred. Compressive strength values for such measures as revealed in the examples varied rather erratically and generally exhibited only small increases in compression strength over the 7-28 day test period. Among the better results were for the preferred mixture wherein the values increased from about 1100 psi at 7 days to 1400 psi at 28 days. The addition of a small amount of calcium chloride added about a 200 psi increment to these values. On the other hand, the addition of 3% of lime stack dust recovered from a lime kiln significantly reduced the results to about 700 psi at 7 days to 900-1300 psi at 28 days. Elimination of the aggregate reduced the strength to a fraction of the values otherwise, a mixture of 12% CKD and 88% fly ash alone showing strength values of only about 190-260 psi over the 28 day test period. Similarly, the choice of a finely divided aggregate such as fill sand resulted in about the same fractional level of strength values in the range of about 140-230 psi. A combination of finely divided and coarse aggregate in approximately equal amounts reduced the compressive strength values by about 1/2 with virtually no change over the test period, giving values ranging from about 650-750 psi, except where 1% of Type 1 portland cement was included which restored the strength values to about their general level, except at the initial 7 day period where the strength values were about 800-900 psi increase at 28 days to about 1200-1600 psi. Curiously, the best strength results were attained when 11.6% fly ash was combined with 3.4% lime with the balance crushed aggregate, the CKD being omitted entirely, for which the strength values while starting at a lower level of about 850-950 at 7 days increased to about 1700 psi at 28 days.
The combination of fly ash and lime stack dust incidentally mentioned in the later patent was explored further by Nicholson in U.S. Pat. No. 4,038,095 which governs mixtures of about 10-14% fly ash, about 5-15% lime stack dust with the balance aggregate in the range of 71-85%. Somewhat inexpicably, the compressive results reported here for such mixtures do not reach the high level specified in the first two patents, the strength values specified being only about 1000 psi with the more general levels well below that depending on particular proportions.
In U.S. Pat. No. 4,268,316, Wills discloses the use of mixtures of kiln dust and fly ash as a replacement for ground limestome and gypsum for forming a mortar or masonry cement, using proportions of about 25-55% portland cement, about 25-65% CKD and 10-25% fly ash. When these mortar formulations were mixed with damp sand in the proportions of about one part cement mixture to 2.5-3 parts sand, compression strengths comparable to those of standard masonry cement composed of 55% cement clinkers, 40% limestone and 5% gypsum were shown for mixtures containing 50% cement, 25-40% CKD and 15-25% fly ash. Inexplicably, in one example, when the cement content was increased to 55% with 35% CKD and 10% fly ash, the compressive strengths dropped by about 30-40% at both the 7 day and 28 day ages to levels inferior to the standard material. As the cement content was decreased, with corresponding increases in the CKD, the compressive strength values dropped drastically. On the other hand, in another similar example mixtures containing 55% cement, 35% CKD and 10% ash proved superior, particularly at the 28 day age, in compressive strength mixtures containing 50% cement, 35% fly ash and 15% CKD as well as other standard masonry cements containing 50% cement, 47% limestone and 3% gypsum. Indeed, strength values dropped about 40% for the mixtures with a 5% reduction in cement and a corresponding 5% increase in the fly ash to values definitely inferior to the standard cements. Similar variations were shown under laboratory test conditions for comparable 50/35/15 mixtures dependent on the source of the fly ash while under actual construction conditions for the same mixtures, compressive strength values were reduced by about 50% for both the conventional masonry cement containing 55% portland cement and comparable mixtures within the patented concept. The fly ash was preferably Class F with Class C materials being less desirable.
In U.S. Pat. No. 4,407,677 Wills went on to teach that in the manufacture of concrete products such as blocks or bricks, the fly ash usually employed in combination with portland cement therein could be replaced in its entirety by CKD with modest improvement in early compressive strength values for such products. Thus, at one day and two day tests, compressive strength values were shown of about 500-800 psi, but were said to increase to about 1200 psi after 28 days. The mixes disclosed here contained 0.4-0.9 parts cement, about 0.1-0.6 parts CKD and 10-12 parts aggregate combining both fine and coarse materials, such as expanded shale and natural sand in a weight ratio of 80/20. Masonry cements generally develop at least about 95% of their strength properties at 28 days age so that additional aging of the patent products would not be expected to result in any significant increase in their compressive strength values.
In a different vein, an improved highly activated fly ash is obtained by Minnick in U.S. Pat. No. 3,643,115 by injecting lime together with bituminous coal into the combustion boiler to give a synthetic fly ash developing early strength as high as five times that obtained conventionally. The improved highly active fly ash can be mixed in proportions of 80-90 parts with 5-87 parts aggregate and 5-30 parts water. The injected lime combines with the sulfur dioxide released during combustion of the coal, and additional sulfur may be needed if the coal has insufficient sulfur, giving a fly ash having a considerably increased sulfate content as well as calcium oxide and magnesium contents.